Benzothiazolemonoazo dyes

ABSTRACT

A monoazo dye of the following formula (I): ##STR1## wherein R is phenyl, phenoxy or benzyl, and D is a group of the formula (D1), (D2), (D3) or (D4): ##STR2## wherein each of X 1 , X 2  and X 3 , which are independent of one another, is hydrogen or chlorine, X 4  is hydrogen, chlorine, methyl or --NHCOR 1 , wherein R 1  is C 1-4  alkyl or phenyl; ##STR3## wherein X 4  is as defined above, Y 1  is hydrogen, chlorine or C 1-4  alkoxy; ##STR4## wherein X 5  is hydrogen, halogen, methyl or --NHZ, wherein Z is C 1-4  alkylsurfonyl, C 1-4  alkylcarbonyl, phenylsulfonyl, phenylcarbonyl, C 1-2  alkoxy C 1-2  alkylcarbonyl or aminocarbonyl, Y 2  is hydrogen, methyl or C 1-2  alkoxy, and Q 1  is cyano or C 1-4  alkylcarbonyl; ##STR5## wherein P is formyl, nitro or cyano, Q 2  is cyano or nitro, T is halogen, methyl, phenyl or methylsulfonyl, X 5  is as defined above, and Y 3  is hydrogen or C 1-2  alkoxy.

This is a Division, of application Ser. No. 08/399,660 filed on Mar. 7,1995 now U.S. Pat. No. 5,527,888.

The present invention relates to water-insoluble monoazo dyes,particularly monoazo dyes suitable for dyeing polyester fibers. Moreparticularly, it relates to red, blue or reddish purple monoazo dyessuitable for dyeing fine denier polyester fibers.

Recently polyester fibers have remarkably advanced toward finer fibersto provide textiles of high added values having comfortable touch orhigh quality, and various fine denier fibers of less than 0.3 d,so-called ultramicro fibers, have been developed and extensively used.However, when ultramicro fibers having small diameters are dyed withconventional dyes, there is a problem that the wet color fastness suchas color fastness to washing substantially decreases.

The object of the present invention is to provide a red, blue or reddishpurple disperse dye capable of giving dyed products having not only goodcolor fastness to washing but also excellent color fastnesses toperspiration (alkali).

The present invention provides a monoazo dye of the following formula(I): ##STR6## wherein R is phenyl, phenoxy or benzyl, and D is a groupof the formula (D1), (D2), (D3) or (D4): ##STR7## wherein each of X¹, X²and X³, which are independent of one another, is hydrogen or chlorine,X⁴ is hydrogen, chlorine, methyl or --NHCOR¹ wherein R¹ is C₁₋₄ alkyl orphenyl; ##STR8## wherein X⁴ is as defined above, Y¹ is hydrogen,chlorine or C₁₋₄ alkoxy; ##STR9## wherein X⁵ is hydrogen, halogen,methyl or --NHZ, wherein Z is C₁₋₄ alkylsulfonyl, C₁₋₄ alkylcarbonyl,phenylsulfonyl, phenylcarbonyl, C₁₋₂ alkoxy C₁₋₂ alkylcarbonyl oraminocarbonyl, Y² is hydrogen, methyl or C₁₋₂ alkoxy, and Q¹ is cyano orC₁₋₄ alkylcarbonyl; ##STR10## wherein P is formyl, nitro or cyano, Q² iscyano or nitro, T is halogen, methyl, phenyl or methylsulfonyl, X⁵ is asdefined above, and Y³ is hydrogen or C₁₋₂ alkoxy.

Now, the present invention will be described in detail.

The monoazo dye of the above formula (I) covers the following four typesof monoazo dyes represented by the formulae (I-1), (I-2), (I-3) and(I-4): ##STR11## wherein X¹, X², X³, X⁴ and R are as defined above;##STR12## wherein X⁴, Y¹ and R are as defined above; ##STR13## whereinX⁵, Y², Q¹ and R are as defined above; ##STR14## wherein P, Q², T, X⁵,Y³ and R are as defined above.

In the formulae (I-1) and (I-2), when X⁴ is --NHCOR¹, C₁₋₄ alkyl for R¹is linear or branched C₁₋₄ alkyl such as methyl, ethyl, n-propyl,i-propyl or n-butyl.

In the formulae (I-3) and (I-4), halogen for T or X⁵ is chlorine orbromine, preferably chlorine. When X⁵ is --NHZ, C₁₋₄ alkylsulfonyl for Zis linear or branched alkylsulfonyl such as methylsulfonyl,ethylsulfonyl, n-propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl orsec-butylsulfonyl.

As C₁₋₄ alkylcarbonyl, C₁₋₄ linear or branched alkylcarbonyl such asmethylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl,n-butylcarbonyl or i-butylcarbonyl may be mentioned.

Among them, C₁₋₂ alkylsulfonyl and C₁₋₂ alkylcarbonyl are particularlypreferred. As C₁₋₂ alkoxy C₁₋₂ alkylcarbonyl for Z,methoxymethylcarbonyl, ethoxymethylcarbonyl, methoxyethylcarbonyl orethoxyethylcarbonyl may be mentioned. Particularly preferred ismethoxymethylcarbonyl. As C₁₋₂ alkoxy for Y² or Y³, methoxy or ethoxymay be mentioned

In the formula (I-3), as C₁₋₄ alkylcarbonyl for Q¹, methylcarbonyl,ethylcarbonyl, n-propylcarbonyl or n-butylcarbonyl may be mentioned.Particularly preferred is C₁₋₂ alkylcarbonyl.

Among the dyes of the present invention represented by the formula (I),the following dyes (1) to (5) are preferred:

(1) a dye of the formula (I-1), wherein X¹ is hydrogen, at least one ofX² and X³ is chlorine, --NHCOR¹ is acetylamino or benzoylamino, and R isphenyl, which is represented by the following formula (I-1-1): ##STR15##wherein one of X²⁻¹ and X³⁻¹ is chlorine, the other is hydrogen, andX⁴⁻¹ is acetylamino or benzoylamino;

(2) a dye of the formula (I-1), wherein X¹ is chlorine, X² and X³ arehydrogen, --NHCOR¹ is acetylamino, and R is phenyl, which is representedby the following formula (I-1-2); ##STR16## (3) a dye of the formula(I-2) wherein X⁴ is hydrogen, methyl or C₁₋₂ alkylcarbonylamino, Y¹ ishydrogen, and R is phenyl, especially a dye of the formula (I-2) whereinX⁴ and Y¹ are hydrogen, and R is phenyl, which is represented by thefollowing formula (I-2-1); ##STR17## (4) a dye of the formula (I-3)wherein X⁵ is C₁₋₂ alkylcarbonylamino or methoxymethylcarbonylamino, Y²is hydrogen, Q¹ is cyano or methylcarbonyl, and R is phenyl;

(5) a dye of the formula (I-4) wherein X⁵ is C₁₋₂ alkylcarbonylamino ormethoxymethylcarbonylamino, Y³ is hydrogen, R is phenyl, P is formyl, Q²is cyano, and T is halogen.

The monoazo dye of the formula (I-1) is prepared, for example, bydiazotizing an amine of the following formula (II): ##STR18## whereinX¹, X² and X³ are as defined above, by a conventional method, followedby coupling with an aniline of the following formula (III): ##STR19##wherein X⁴ and R are as defined above.

The monoazo dye of the formula (I-2) is prepared, for example, bydiazotizing 2-amino-6-nitrobenzothiazole by a conventional method,followed by coupling with an aniline of the following formula (IV):##STR20## wherein X⁴, Y¹ and R are as defined above.

The monoazo dye of the formula (I-3) is prepared, for example, bydiazotizing an amine of the following formula (V): ##STR21## wherein Q¹is as defined above, by a conventional method, followed by coupling withan aniline of the following formula (VI): ##STR22## wherein X⁵, Y² and Rare as defined above

The monoazo dye of the formula (I-4) is prepared, for example, bydiazotizing an amine of the following formula (VII): ##STR23## whereinP, Q² and T are as defined above, by a conventional method, followed bycoupling with an aniline of the following formula (VIII): ##STR24##wherein X⁵, Y³ and R are as defined above

Textile materials to which the monoazo dye of the present invention isapplicable, include polyester fibers made of polyethylene terephthalate,polybutylene terephthalate or a polycondensate of terephthalic acid and1,4-bis-(hydroxymethyl)cyclohexane, polyamide fibers made of nylon andthe like, and fiber blend products such as blended yarn fabrics andunion cloths comprising natural fibers such as cotton, silk and woolfibers and the above mentioned polyester fibers.

Particularly, among polyester fibers, not only ordinary polyester fibers(regular denier fibers) but also microfibers (fine denier fibers, whichare less than 1 d) and ultramicro fibers (which are less than 0.3 d) maybe mentioned as fibers which can successfully be dyed with the monoazodye of the present invention.

When the monoazo dye of the present invention is used in dyeing, themonoazo dye of the formula (I) is dispersed in an aqueous medium bymeans of a dispersing agent in the usual way to prepare a dye bath fordyeing or a printing paste for textile printing.

For example, in the case of dyeing, polyester fibers and fiber mixtureproducts such as blended yarn fabrics of union cloth product comprisingpolyester fibers can be dyed with good color fastness by common dyeingmethods, such as a high temperature dyeing method, a carrier dyeingmethod and a thermosol dyeing method. In some cases, the addition of anacidic substance to the dyeing bath may result in more successfuldyeing.

Dyed products obtained by dyeing or textile printing with the monoazodye of the present invention are excellent in not only color fastness towashing but also various color fastnesses such as color fastnesses toperspiration (alkali), to sublimation and to water. Further, even if thedyed produces are further processed, no substantial decrease in the wetcolor fastness occurs.

The monoazo dye of the present invention may be used in combination withsimilar or other types of dyes.

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted by such specific Examples.

EXAMPLE 1

0.025 g of a 1:1 monoazo dye mixture of the monoazo dyes of thefollowing formulae (I-1-3) and (I-1-4): ##STR25## which are covered bythe formula (I-1) wherein X⁴ is --NHCOCH₃ and R is phenoxy, wasdispersed in 200 ml of water containing 0.025 g of a naphthalenesulfonicacid-formaldehyde condensate and 0.025 g of a sulfuric acid ester of ahigher alcohol to prepare a dye bath. In the dye bath, 10 g of a unioncloth comprising polyester fibers of 2d and 0.01 d was immersed fordyeing at 135° C. for 30 minutes. After the dyeing, the cloth wassubjected to soaping, washed with water and dried, whereby a brilliantred well-dyed cloth was obtained with the different denier polyesterfibers dyed with the same color and the same color strength. The colorfastness to washing of the union cloth-dyed with the dye mixture was asexcellent as 4-5 grade.

The color fastness to washing was measured in accordance with the AATCC2A method and evaluated by the degree of staining on a nylon cloth.

The dye mixture used in this Example was prepared as follows. 4.4 g of a1:1 mixture of 5,6-dichloroaminobenzothiazole and6,7-dichloroaminobenzothiazole was dissolved in 80 g of a 50% sulfuricacid aqueous solution at 80° C. and then cooled to 0° C. Then, 6.5 g ofa 43% nitrosylsulfuric acid was added to the solution at 0° C. and thesolution was stirred for 2 hours to obtain a diazo liquid.

After 9.0 g of N,N-diphenoxycarbonyloxyethyl-m-acetylaminoaniline wasdissolved in 200 ml of methanol, the diazo liquid was dropwise addedthereto at 0° to 5° C. followed by stirring for 2 hours. The product wascollected by filtration, washed with water and dried to obtain thedesired dye mixture. The wavelength at the maximum absorption of the dyemixture (λ^(max) : in acetone) was 530 nm.

COMPARATIVE EXAMPLE 1

The compound having the same basic chemical structure as represented bythe formula (I-1) wherein X⁴ is --NHCOCH₃ and R is ethoxy (dye used inExample 1 in Japanese Unexamined Patent Publication No.255601/1993), wassynthesized in accordance with the method in Example 1, and anultramicro fiber union cloth was dyed therewith. The dyed cloth wasevaluated in the same manner as in Example 1. The color fastness towashing of the dyed cloth was as poor as 3 grade.

EXAMPLES 2 TO 25

The dyes shown in Tables 1 and 2 were synthesized, and ultramicro fiberunion cloths were dyed therewith. The color fastnesses to washing of thedyed cloths were measured in the same manner as in Example 1. Theresults are shown in Tables 1 and 2.

                                      TABLE 1                                     __________________________________________________________________________    The 1:1 mixture of the dyes of the formulae (I-1-5) and (I-1-6)                ##STR26##                        (I-1-5)                                      ##STR27##                        (I-1-6)                                                                λ.sub.max                                                                   Color                                                                    (nm; in                                                                            fastness to                                   Example                                                                            X.sup.4     R         Acetone)                                                                           washing                                       __________________________________________________________________________    2    NHCOCH.sub.3                                                                               ##STR28##                                                                              543  4-5                                           3    NHCOCH.sub.3                                                                               ##STR29##                                                                              545  4-5                                                 ##STR30##                                                                                 ##STR31##                                                                              542  4-5                                           5    NHCOC.sub.2 H.sub.5                                                                        ##STR32##                                                                              542  4-5                                           6    NHCOC.sub.3 H.sub.7 (n)                                                                    ##STR33##                                                                              542  4-5                                           7    NHCOC.sub.4 H.sub.9 (n)                                                                    ##STR34##                                                                              542  4-5                                           8    Cl                                                                                         ##STR35##                                                                              504  4-5                                           9    CH.sub.3                                                                                   ##STR36##                                                                              526  4-5                                           10   H                                                                                          ##STR37##                                                                              514  4-5                                           __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR38##                                                                                                        λ.sub.max                                                                   Color                                                                    (nm: in                                                                            fastness                             Example                                                                            X.sup.1                                                                          X.sup.2                                                                          X.sup.3                                                                          X.sup.4     R         Acetone)                                                                           to washing                           __________________________________________________________________________    11   Cl H  H  NHCOCH.sub.3                                                                               ##STR39##                                                                              546  4-5                                  12   Cl H  H  NHCOCH.sub.3                                                                               ##STR40##                                                                              544  4-5                                  13   Cl H  H  NHCOCH.sub.3                                                                               ##STR41##                                                                              547  4-5                                  14   Cl H  H  Cl                                                                                         ##STR42##                                                                              507  4-5                                  15   Cl H  H  H                                                                                          ##STR43##                                                                              517  4-5                                  16   Cl H  H  CH.sub.3                                                                                   ##STR44##                                                                              529  4-5                                  17   H  H  H  NHCOCH.sub.3                                                                               ##STR45##                                                                              524  4                                    18   H  H  H  Cl                                                                                         ##STR46##                                                                              500  4                                    19   H  H  H  H                                                                                          ##STR47##                                                                              510  4                                    20   H  H  H  CH.sub.3                                                                                   ##STR48##                                                                              521  4                                    21   H  H  H                                                                                 ##STR49##                                                                                 ##STR50##                                                                              523  4-5                                  22   H  H  H  NHCOC.sub.3 H.sub.7 (n)                                                                    ##STR51##                                                                              525  4-5                                  23   Cl Cl H  NHCOCH.sub.3                                                                               ##STR52##                                                                              532  4-5                                  24   Cl Cl H  H                                                                                          ##STR53##                                                                              518  4-5                                  25   Cl Cl H  H                                                                                          ##STR54##                                                                              516  4-5                                  __________________________________________________________________________

EXAMPLE 26

0.025 g Of the monoazo dye of the following formula (I-2-1) whichcorresponds to the formula (I-2) wherein X⁴ and Y¹ are hydrogen, and Ris phenyl: ##STR55## was dispersed in 200 ml of water containing 0.025 gof a naphthalenesulfonic acid-formaldehyde condensate and 0.025 g of asulfuric acid ester of a higher alcohol to prepare a dye bath. 10 g of aunion cloth comprising polyester fibers of 2 d and 0.01 d was immersedin the dye bath at 135° C. for 30 minutes for dyeing, and then the clothwas subjected to soaping, washed with water and dried, whereby abrilliant red well-dyed cloth was obtained with the different denierfibers dyed with the same color and the same color strength. The colorfastness to washing of the union cloth dyed with the dye was as aexcellent as 4 to 5 grade.

The color fastness to washing was measured in accordance with the AATCC2A method and evaluated by the degree of staining on a nylon cloth.

The dye used in this Example was prepared as follows.

10.0 g of 2-amino-6-nitrobenzothiazole was added to a liquid mixture of45 g of 75% phosphoric acid, 16 g of acetic acid and 8.5 g of sulfuricacid, and 16 g of 43% nitrosylsulfuric acid was dropwise added theretoat -2° C. followed by stirring for 2 hours to obtain a diazo liquid.

After 19.0 g of N,N-diphenylcarbonyloxyethylaniline was dissolved in 800ml of methanol, the diazo liquid was dropwise added thereto at 0° to 5°C. The mixture was stirred for 2 hours. The product was collected byfiltration, washed with water and dried to obtain the desired dye. Thewavelength at the maximum absorption of the dye (λ_(max) : in acetone)was 530 nm.

COMPARATIVE EXAMPLE 2

The compound of the formula (I-2) wherein each of X⁴ and Y¹ is hydrogenand R is methyl (as disclosed in Japanese Examined Patent PublicationNo. 16039/1961) was synthesized in accordance with the method in Example26, and an ultramicro fiber union cloth was dyed therewith and the dyedcloth was evaluated in the same manner as in Example 26. The colorfastness to washing of the dyed cloth was as poor as 3 grade.

EXAMPLES 27 TO 41

The dyes shown in Table 3 were synthesized in the same manner as inExample 26. Ultramicro fiber union cloths were dyed therewith, and thecolor fastness to washing was measured in the same manner as in Example26.

The results are shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________     ##STR56##                                                                                                 λ.sub.max                                                                   Color                                                                    (nm; in                                                                            fastness                                    Example                                                                            X.sup.4  Y.sup.1                                                                            R         Acetone)                                                                           to washing                                  __________________________________________________________________________    27   H        H                                                                                   ##STR57##                                                                              532  4-5                                         28   H        H                                                                                   ##STR58##                                                                              528  4-5                                         29   CH.sub.3 H                                                                                   ##STR59##                                                                              542  4-5                                         30   CH.sub.3 H                                                                                   ##STR60##                                                                              544  4-5                                         31   CH.sub.3 H                                                                                   ##STR61##                                                                              540  4-5                                         32   Cl       H                                                                                   ##STR62##                                                                              520  4-5                                         33   Cl       H                                                                                   ##STR63##                                                                              518  4-5                                         34   H        Cl                                                                                  ##STR64##                                                                              510  4-5                                         35   H        Cl                                                                                  ##STR65##                                                                              508  4-5                                         36   NHCOCH.sub.3                                                                           H                                                                                   ##STR66##                                                                              550  4-5                                         37   NHCOCH.sub.3                                                                           H                                                                                   ##STR67##                                                                              548  4-5                                         38   NHCOCH.sub.3                                                                           H                                                                                   ##STR68##                                                                              552  4-5                                         39   NHCOC.sub.3 H.sub.7 (n)                                                                H                                                                                   ##STR69##                                                                              550  4-5                                         40   NHCOC.sub.3 H.sub.7 (n)                                                                OCH.sub.3                                                                           ##STR70##                                                                              570  4-5                                         41   NHCOCH.sub.3                                                                           OCH.sub.3                                                                           ##STR71##                                                                              572  4-5                                         __________________________________________________________________________

EXAMPLE 42 ##STR72##

0.025 g of the monoazo dye of the above formula was dispersed in 200 mlof water containing 0.025 g of a naphthalenesulfuric acid-formaldehydecondensate and 0.025 g of a sulfuric acid ester of a higher alcohol toprepare a dye bath. 10 g of a union cloth comprising polyester fibers of2 d and 0.01 d was immersed for dyeing at 135° C. for 30 minutes, andthen the cloth was subjected to soaping, washed with water and dried,whereby a brilliant blue well-dyed cloth with the different denierfibers dyed in the same color and with the same color strength wasobtained. The color fastness to washing of the union cloth dyed with thedye was as excellent as 4⁺ grade.

The color fastness to washing was measured by the AATCC 2A method andevaluated by the degree of staining on a nylon cloth.

The monoazo dye used in this Example was prepared as follows.

0.76 g of sodium nitrite was added to 5 g of sulfuric acid, and theresulting mixture was heated to 70° C. and then cooled to 5° C. Amixture of 1.4 g of propionic acid and 8.6 g of acetic acid wasgradually added thereto, and the temperature was elevated to 15° C. andmaintained at this level. After the solution was cooled to 0° C., 1.7 gof 2-amino-3-cyano-5-nitrothiophene and then 1.4 g of propionic acid and8.6 g of acetic acid were added to the solution, and the resultingmixture was stirred at 5° C. for 75 minutes. To the mixture, the sameamounts of propionic and acetic acid were added, and the mixture wasfurther stirred at 5° C. for one hour.

Urea was added to the mixture to decompose the remaining nitrous acid,and the resulting diazonium salt solution was dropwise added to asolution of 4.5 g of N,N-dibenzoyloxyethylamino-m-acetoanilide in 200 mlof methanol at 0° to 5° C. and the solution was stirred for 2 hours. Thedesired dye was separated from the solution by filtration, washed withwaster and dried.

The wavelength at the maximum absorption of the dye (λ_(max) : inacetone) was 606 nm.

COMPARATIVE EXAMPLE 3

The dye of the following formula: ##STR73## as disclosed in Example 80in Japanese Examined Patent Publication No. 47214/1982, was evaluated inthe same manner as in Example 42, and the color fastness to washing wasas poor as 2 to 3 grade.

EXAMPLES 43 TO 74

The dyes shown in Table 4 were synthesized in accordance with the methodin Example 42, and ultramicro fiber union cloths were dyed in the samemanner as in Example 42.

The color fastness to washing of all the dyes were at least 4⁺ grade.

                                      TABLE 4                                     __________________________________________________________________________     ##STR74##                                                                                                             λ.sub.max                                                                    Hue of dyed                    Example                                                                            Q.sup.1 X.sup.5     Y.sup.2                                                                             R         (Acetone)                                                                           cloth                          __________________________________________________________________________    43   CN      NHCOC.sub.2 H.sub.5                                                                       H                                                                                    ##STR75##                                                                              605   moderate blue                  44   CN      NHCOC.sub.4 H.sub.9(n)                                                                    H                                                                                    ##STR76##                                                                              601   moderate blue                  45   CN      NHCOCH.sub.2 OCH.sub.3                                                                    H                                                                                    ##STR77##                                                                              604   moderate blue                  46   CN      NHCOC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                      H                                                                                    ##STR78##                                                                              604   moderate blue                  47   CN      NHCOCH.sub.3                                                                              OCH.sub.3                                                                            ##STR79##                                                                              642   bluish green                   48   CN      CH.sub.3    H                                                                                    ##STR80##                                                                              613   reddish blue                   49   CN      CH.sub.3    H                                                                                    ##STR81##                                                                              610   reddish blue                   50   CN      CH.sub.3    H                                                                                    ##STR82##                                                                              615   reddish blue                   51   CN      CH.sub.3    OC.sub.2 H.sub.5                                                                     ##STR83##                                                                              645   bluish green                   52   CN                                                                                     ##STR84##  H                                                                                    ##STR85##                                                                              601   moderate blue                  53   CN      NHSO.sub.2 CH.sub.3                                                                       H                                                                                    ##STR86##                                                                              592   moderate blue                  54   CN      NHSO.sub.2 C.sub.2 H.sub.5                                                                H                                                                                    ##STR87##                                                                              589   moderate blue                  55   CN                                                                                     ##STR88##  H                                                                                    ##STR89##                                                                              588   moderate blue                  56   CN      NHCOC.sub.3 H.sub.7 (i)                                                                   H                                                                                    ##STR90##                                                                              607   greenish blue                  57   CN      NHCOC.sub.3 H.sub.7 (n)                                                                   CH.sub.3                                                                             ##STR91##                                                                              585   dark blue                      58   CN      Cl          H                                                                                    ##STR92##                                                                              594   reddish blue                   59   CN      Cl          H                                                                                    ##STR93##                                                                              591   reddish blue                   60   CN      Br          H                                                                                    ##STR94##                                                                              590   reddish blue                   61   CN      NHCONH.sub.2                                                                              H                                                                                    ##STR95##                                                                              609   greenish blue                  62   CN      NHCONH.sub.2                                                                              H                                                                                    ##STR96##                                                                              606   greenish blue                  63   CN      NHCONH.sub.2                                                                              H                                                                                    ##STR97##                                                                              611   greenish blue                  64   CN      CH.sub.3    H                                                                                    ##STR98##                                                                              614   reddish blue                   65   CN      CH.sub.3    CH.sub.3                                                                             ##STR99##                                                                              595   dark blue                      66   CN      H           H                                                                                    ##STR100##                                                                             604   reddish blue                   67   CN      H           H                                                                                    ##STR101##                                                                             601   reddish blue                   68   CN      H           OCH.sub.3                                                                            ##STR102##                                                                             629   moderate blue                  69   CN      CH.sub.3    OCH.sub.3                                                                            ##STR103##                                                                             639   greenish blue                  70                                                                                  ##STR104##                                                                           CH.sub.3    H                                                                                    ##STR105##                                                                             630   reddish blue                   71                                                                                  ##STR106##                                                                           NHCOCH.sub.3                                                                              H                                                                                    ##STR107##                                                                             598   moderate blue                  72                                                                                  ##STR108##                                                                           NHCOCH.sub.2 OCH.sub.3                                                                    H                                                                                    ##STR109##                                                                             596   moderate blue                  73                                                                                  ##STR110##                                                                           NHSO.sub.2 C.sub.2 H.sub.5                                                                OCH.sub.3                                                                            ##STR111##                                                                             624   bluish green                   74                                                                                  ##STR112##                                                                            ##STR113## OCH.sub.3                                                                            ##STR114##                                                                             636   bluish green                   __________________________________________________________________________

EXAMPLE 75 ##STR115##

0.025 g of the monoazo dye of the above formula was dispersed in 200 mlof water containing 0.025 g of a naphthalenesulfuric acid-formaldehydecondensate and 0.025 g of a sulfuric acid ester of a higher alcohol toprepare a dye bath. 10 g of a union cloth comprising polyester fibers of2 d and 0.01 d was immersed for dyeing at 135° C. for 30 minutes, andthen the cloth was subjected to soaping, washed with water and dried,whereby a brilliant blue well-dyed cloth with the different denierfibers dyed in the same color and with the same color strength wasobtained. The color fastness to washing of the union cloth dyed with thedye was as excellent as 4⁺ grade.

The color fastness to washing was measured by the AATCC 2A method andevaluated by the degree of staining on a nylon cloth.

The monoazo dye used in this Example was prepared as follows.

To a mixture of 15 g of glacial acetic acid/propionic acid (3:1) and 5.0g of 85% sulfuric acid, 1.9 g of2-amino-3-cyano-4-chloro-5-formylthiophene was added and then 3.2 g ofnitrosylsulfuric acid (43%) was dropwise added at 0°0 to 5° C. Theresulting solution was stirred at 0° to 5° C. for 4 hours.

Urea was added to the solution to decompose the residual nitrous acid,and the resulting solution was dropwise added to a solution of 4.5 g ofN,N-dibenzoyloxyethylamino-m-acetoanilide in 200 ml of methanol at 0° to5° C. The solution was stirred for 2 hours and filtered to collect thedesired dye, and it was washed with water and dried.

The wavelength at the maximum absorption of the dye (λ_(max) : inacetone) was 590 nm.

COMPARATIVE EXAMPLE 4

The dye disclosed in Example 6 in Japanese Unexamined Patent PublicationNo. 266466/1986 of the following formula: ##STR116## was evaluated inaccordance with Example 75. As a result, the color fastness to washingwas as poor as 2 to 3 grade.

EXAMPLES 76 TO 95

The dyes shown in Table 5 were synthesized in accordance with the methodin Example 75, and ultramicro fiber union cloths were dyed in the samemanner as in Example 75. The color fastnesses to washing were at least4⁺.

                                      TABLE 5                                     __________________________________________________________________________     ##STR117##                                                                                                                   λ.sub.max                                                              nm                            Example                                                                            P    Q.sup.2                                                                           T      X.sup.5     Y.sup.3                                                                            R         (Acetone)                                                                           Hue                     __________________________________________________________________________    76   CHO  CN  Cl     NHCOCH.sub.3                                                                              H                                                                                   ##STR118##                                                                             576   reddish blue            77   CHO  CN  Cl     NHCONH.sub.2                                                                              H                                                                                   ##STR119##                                                                             593   moderate blue           78   CHO  CN  Cl     NHCOC.sub.2 H.sub.4 OCH.sub.3                                                             H                                                                                   ##STR120##                                                                             592   moderate blue           79   CHO  CN  Cl     H           H                                                                                   ##STR121##                                                                             573   violet                  80   CHO  CN  Cl     CH.sub.3    H                                                                                   ##STR122##                                                                             584   bluish violet           81   CHO  CN  Cl     Cl          H                                                                                   ##STR123##                                                                             569   violet                  82   CHO  CN  Cl     NHCOCH.sub.3                                                                              OCH.sub.3                                                                           ##STR124##                                                                             622   bluish green            83   CHO  NO.sub.2                                                                          Cl     NHSO.sub.2 CH.sub.3                                                                       H                                                                                   ##STR125##                                                                             546   violet                  84   CHO  CN                                                                                 ##STR126##                                                                          CH.sub.3    H                                                                                   ##STR127##                                                                             582   bluish violet           85   CHO  CN                                                                                 ##STR128##                                                                          NHCOCH.sub.3                                                                              H                                                                                   ##STR129##                                                                             592   moderate blue           86   CHO  CN  Br                                                                                    ##STR130## H                                                                                   ##STR131##                                                                             572   bluish violet           87   CHO  CN  SO.sub.2 CH.sub.3                                                                    NHCOC.sub.4 H.sub.9                                                                       H                                                                                   ##STR132##                                                                             601   moderate blue           88   NO.sub.2                                                                           CN  Cl     CH.sub.3    H                                                                                   ##STR133##                                                                             614   reddish blue            89   NO.sub.2                                                                           CN  Cl     NHCOCH.sub.3                                                                              H                                                                                   ##STR134##                                                                             618   moderate blue           90   NO.sub.2                                                                           CN  Cl     NHSO.sub.2 C.sub.2 H.sub.5                                                                OCH.sub.3                                                                           ##STR135##                                                                             643   bluish green            91   NO.sub.2                                                                           CN  Br     NHCOC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                      H                                                                                   ##STR136##                                                                             621   moderate blue           92   CN   CN  Cl     CH.sub.3    OC.sub.2 H.sub.5                                                                    ##STR137##                                                                             639   bluish green            93   CN   CN  CH.sub.3                                                                              ##STR138## H                                                                                   ##STR139##                                                                             565   violet                  94   CN   CN  CH.sub.3                                                                             NHCOC.sub.4 H.sub.9                                                                       OCH.sub.3                                                                           ##STR140##                                                                             603   reddish blue            95   CN   CN  CH.sub.3                                                                             Br          H                                                                                   ##STR141##                                                                             539   reddish                 __________________________________________________________________________                                                          violet              

The present invention provides dyes capable of dyeing polyester fiberswith excellent color fastnesses to perspiration (alkali), to sublimationand to water. The present invention provides-disperse dyes capable ofdyeing polyester ultramicro fibers which are difficult to dye, with red,blue or reddish violet with excellent color fastness.

We claim:
 1. A monoazo dye of the following formula (I): ##STR142##wherein R is phenyl, phenoxy or benzyl, and D is a group of the formula(D1) or (D2): ##STR143## wherein each of X¹, X² and X³, which areindependent of one another, is hydrogen or chlorine, X⁴ is hydrogen ,chlorine, methyl or --NHCOR¹, wherein R¹ is C₁₋₄ alkyl or phenyl;##STR144## wherein X⁴ is as defined above, Y¹ is hydrogen, chlorine orC₁₋₄ alkoxy.
 2. The monoazo dye according to claim 1, which isrepresented by the following formula (I-1): ##STR145## wherein X¹, X²,X³, X⁴ and R are as defined above.
 3. The monoazo dye according to claim2, which is represented by the following formula (I-1-1): ##STR146##wherein one of X²⁻¹, and X³⁻¹ is chlorine, the other is hydrogen, andX⁴⁻¹ is acetylamino or benzoylamino.
 4. The monoazo dye according toclaim 2, which is represented by the following formula (I-1-2):##STR147##
 5. The monoazo dye according to claim 1, which is representedby the following formula (I-2): ##STR148## wherein X⁴, Y¹ and R are asdefined above.
 6. The monoazo dye according to claim 5, wherein X⁴ ishydrogen, methyl or C₁₋₂ alkylcarbonylamino, Y¹ is hydrogen, and R isphenyl.
 7. The monoazo dye according to claim 1, which is represented bythe following formula (I-2-1): ##STR149##
 8. A method for dyeingpolyester ultramicro fibers by applying thereto the monoazo dye ofclaim
 1. 9. Polyester ultramicro fibers dyed with the monoazo dye ofclaim 1.